EP0859404A2 - Waschlösung für Halbleiter-Substraten und Waschmethode - Google Patents

Waschlösung für Halbleiter-Substraten und Waschmethode Download PDF

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Publication number
EP0859404A2
EP0859404A2 EP98100625A EP98100625A EP0859404A2 EP 0859404 A2 EP0859404 A2 EP 0859404A2 EP 98100625 A EP98100625 A EP 98100625A EP 98100625 A EP98100625 A EP 98100625A EP 0859404 A2 EP0859404 A2 EP 0859404A2
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EP
European Patent Office
Prior art keywords
acid
washing
weight
solution
semiconductor substrate
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EP98100625A
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English (en)
French (fr)
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EP0859404B1 (de
EP0859404A3 (de
Inventor
Chizuko Matsuo
Mikio c/o Central Research Institute Kishimoto
Kazushige Takaishi
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Mitsubishi Materials Silicon Corp
Mitsubishi Materials Corp
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Mitsubishi Materials Silicon Corp
Mitsubishi Materials Corp
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Priority claimed from JP561197A external-priority patent/JPH10209100A/ja
Priority claimed from JP00561297A external-priority patent/JP3354822B2/ja
Application filed by Mitsubishi Materials Silicon Corp, Mitsubishi Materials Corp filed Critical Mitsubishi Materials Silicon Corp
Publication of EP0859404A2 publication Critical patent/EP0859404A2/de
Publication of EP0859404A3 publication Critical patent/EP0859404A3/de
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Publication of EP0859404B1 publication Critical patent/EP0859404B1/de
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02041Cleaning
    • H01L21/02043Cleaning before device manufacture, i.e. Begin-Of-Line process
    • H01L21/02052Wet cleaning only
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22Organic compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D2111/00Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10Objects to be cleaned
    • C11D2111/14Hard surfaces
    • C11D2111/22Electronic devices, e.g. PCBs or semiconductors

Definitions

  • This invention relates to a washing solution for washing the surface of a semiconductor substrate such as a silicon wafer and a washing method using the same.
  • an RCA washing method using an SC1 solution comprising hydrogen peroxide and ammonium hydroxide, and an SC2 solution comprising hydrogen peroxide and a diluted hydrochloric acid.
  • a semiconductor substrate is firstly immersed in the SC1 solution to remove fine particles and organic residue from the substrate by the oxidizing and alkaline properties of the solution. That is, in the SC1 solution, both reactions of oxidization and reduction are simultaneously carried out, and reduction due to ammonia and oxidization due to hydrogen peroxide occur in the same bath competitively, and simultaneously, fine particles are removed from the substrate surface by lifting off due to an etching effect of the ammonium hydroxide solution. Then, the semiconductor substrate is immersed in an acidic solution of the SC2 solution to remove alkali ions or metal impurities which are insoluble in the SC1 solution.
  • Japanese Laid-Open Patent Application No. 94458/1995 discloses a washing solution of a semiconductor substrate which prevents metal impurities in a washing solution from adhering to the substrate surface when the semiconductor substrate is washed or prevents metal impurities once removed from the substrate surface from adhering to the substrate surface again, and inhibits unnecessary growth of a naturally oxidized film, and a washing method using the same.
  • This washing solution is constituted by an acidic solution such as hydrofluoric acid containing 0.0001 to 0.001 % by weight of ammonia or 0.0005 to 0.01 % by weight of ethylenediaminetetraacetic acid (EDTA).
  • pH thereof is maintained to 1 or so in order to remove an oxidized film.
  • this washing method when a semiconductor substrate 1 is immersed in a washing solution 5 as shown in Fig. 6, removal of a naturally oxidized film 2 and removal of metal impurities 4 are simultaneously proceed, and a metal element shifted over to the washing solution forms a complex, or a metal complex salt 7 whereby it is masked.
  • the surface of the semiconductor substrate 1 is charged to minus in the acidic solution while the surface of the metal complex salt 7 is also charged to minus by forming a complex ion in the acidic solution so that the metal complex salt, i.e., a metal element is prevented from adhering again to the substrate.
  • the above-mentioned RCA washing method occurs two reactions of oxidation and reduction in the same bath competitively.
  • metal impurities liberated from the substrate surface is retained in the SC1 solution whereby they are sometimes adhered again to the substrate surface depending on the surface potential, and secondly, even when a metal complex salt is to be formed by complexing metal ions in the SC1 solution, an organic acid is subjected to oxidization-reduction treatment in the SC1 solution whereby its complexing effect is markedly lowered. Accordingly, there is a problem that metal impurities cannot sufficiently be removed by the RCA washing method depending on the kind of a metal.
  • An object of the present invention is to provide a washing solution of a semiconductor substrate for removing well both of metal impurities and fine particles adhered to the surface of the semiconductor substrate and a washing method using the same.
  • An invention of Claim 1 relates to a washing solution of a semiconductor device containing 0.0001 to 0.1 % by weight of an organic acid and 0.005 to 0.25 % by weight of hydrofluoric acid and having pH of 2 to 4.
  • An invention of Claim 2 is an invention relating to Claim 1 and comprises a washing solution wherein the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, ethylenediaminetetraacetic acid (hereinafter abbreviated to as EDTA), tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, ethylenediaminetetraacetic acid (hereinafter abbreviated to as EDTA), tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • An invention of Claim 4 is an invention relating to Claim 3 and comprises a washing method wherein the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, EDTA, tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • Fig. 1 is a drawing showing a washing mechanism when washing is carried out by using a washing solution according to Claim 1 of the present invention.
  • Fig. 2 is a drawing showing another washing mechanism when washing is carried out by using a washing solution according to Claim 1 of the present invention.
  • Fig. 4 is a drawing showing a removing effect of Fe in Example and Comparative example when wavelength of an irradiated light is changed.
  • Fig. 5 is a drawing showing a metal impurity concentration at a wafer surface after washing in Example 47 and Comparative example 7.
  • Fig. 6 is a drawing showing a washing mechanism when washing is carried out by using the conventional washing solution.
  • a contaminated semiconductor substrate 11 is immersed in a washing solution 15.
  • a naturally oxidized film 12 formed on the surface of the semiconductor substrate 11 is removed by hydrofluoric acid (HF) whereby fine particles 13 and metal impurities 14 on the naturally oxidized film 12 as well as metal impurities 14 contained in the naturally oxidized film are shifted over to the washing solution 15.
  • the washing solution 15 is an acidic solution having pH of 2 to 4 and containing 0.005 to 0.25 % by weight of hydrofluoric acid and 0.0001 to 0.1 % by weight of an organic acid, the surfaces of the fine particles 13 are charged to minus which is the same as that of the surface of the substrate 11.
  • the metal impurities 14 liberated into the solution form a complex with organic acid molecules 16 to yield metal complex salts 17.
  • This complex ion of the metal complex salt 17 is a minus ion.
  • both of the surface potentials of the fine particles 13 and the metal impurities 14 become minus which is the same as that of the substrate 11 whereby adhesion or readhesion to the substrate can be prevented (Fig. 1(c)).
  • a substrate 11 the surface of which is cleaned can be obtained (Fig. 1(d)).
  • An invention according to Claim 5 relates to a method of washing a semiconductor substrate which comprises washing a semiconductor substrate with a washing solution containing 0.0001 to 0.1 % by weight of an organic acid and having pH of 2 to 4 while irradiating light with a wavelength of at least 500 nm.
  • a contaminated semiconductor substrate is immersed in a washing solution and light with a wavelength of at least 500 nm is irradiated to the surface of the substrate.
  • a washing solution By immersing the substrate in a washing solution, fine particles and metal impurities adhered to the substrate surface shift over to the washing solution.
  • the washing solution is an acidic solution having pH of 2 to 4 and containing 0.0001 to 0.1 % by weight of an organic acid, the surfaces of the fine particles are charged to minus which is the same as that of the surface of the substrate.
  • both of the surface potentials of the fine particles and the metal impurities become minus which is the same as that of the substrate whereby adhesion or re-adhesion to the substrate can be prevented.
  • An invention according to Claim 6 relates to a method of washing a semiconductor substrate which comprises washing a semiconductor substrate with a washing solution containing 0.0001 to 0.1 % by weight of an organic acid and 0.005 to 0.25 % by weight of hydrofluoric acid and having pH of 2 to 4 while irradiating light with a wavelength of at least 500 nm.
  • a contaminated semi-conductor substrate 11 is immersed in a washing solution 15 and light 20 with a wavelength of at least 500 nm is irradiated to the surface of the substrate 11.
  • hydrofluoric acid HF
  • hydrofluoric acid removes a naturally oxidized film 12 formed on the surface of the semiconductor substrate 11, and fine particles 13 and metal impurities 14 on the naturally oxidized film 12 as well as metal impurities 14 contained in the naturally oxidized film are shifted over to the washing solution 15.
  • the washing solution 15 is an acidic solution having pH of 2 to 4 and containing 0.005 to 0.25 % by weight of hydrofluoric acid and 0.0001 to 0.1 % by weight of an organic acid
  • the surfaces of the fine particles 13 are charged to minus which is the same as that of the substrate surface 11.
  • the metal impurities 14 liberated into the solution form a complex with organic acid molecules 16 to yield metal complex salts 17.
  • This complex ion of the metal complex salt 17 is a minus ion.
  • both of the surface potentials of the fine particles 13 and the metal impurities 14 become minus which is the same as that of the substrate 11 whereby adhesion or re-adhesion to the substrate can be prevented (Fig. 3(c)).
  • An invention relating to Claim 7 is an invention according to Claim 5 or 6 and relates to a washing method wherein the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, EDTA, tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, EDTA, tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • a method of Claim 8 relates to a washing method of a semiconductor substrate which contains a first washing step of washing a semiconductor substrate with a mixed solution of an organic acid and hydrofluoric acid with pH of 2 to 4, and a second washing step of washing said semiconductor substrate with an oxidizing solution.
  • An invention relating to Claim 9 is an invention according to Claim 8, and is a method of washing a semiconductor substrate wherein the first washing step and the second washing step are each carried out at least twice.
  • the surface of the substrate can be more cleaned.
  • An invention according to Claim 10 is an invention relating to Claim 8 or 9, and is a method of washing a semiconductor substrate wherein the mixed solution of the first washing step contains 0.0001 to 0.1 % by weight of an organic acid and 0.005 to 0.25 % by weight of hydrofluoric acid.
  • an organic acid and hydrofluoric acid in the above-mentioned concentration ranges are preferred.
  • An invention according to Claim 11 is an invention relating to Claim 8 or 10, and is a method of washing a semiconductor substrate wherein the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, EDTA, tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • the organic acid is one or more organic acid selected from the group consisting of citric acid, succinic acid, EDTA, tartaric acid, salicylic acid, oxalic acid, acetic acid and formic acid.
  • organic acids enumerated have a complexing action of metal ions which are impurities contaminating the substrate.
  • An invention according to Claim 12 is an invention relating to Claim 8 or 9, and is a method of washing a semiconductor substrate wherein the semiconductor substrate is subjected to ultrasonic washing with the mixed solution of the first washing step.
  • the enumerated oxidizing solutions as mentioned above have actions of forming an oxidizing film at the surface of the substrate and of decomposing and removing organic acids or organic substances adhered to the surface of the substrate.
  • a kind of an organic acid and a concentration thereof are determined depending on the kind of metal impurities to be removed.
  • pH of the washing solution is 2 to 4.
  • a concentration of the organic acid in the washing solution is 0.0001 to 0.1 % by weight, preferably 0.003 to 0.006 % by weight. If it is less than 0.0001 % by weight, a complexing action of metal impurity ions liberated from the surface of the substrate is not sufficient, while if it exceeds 0.1 % by weight, there is a disadvantage that an amount of fine particles adhered again will increase.
  • organic acid of the present invention in addition to citric acid, succinic acid, EDTA, suitable for the present invention are tartaric acid, salicylic acid, oxalic acid, acetic acid, formic acid and the like.
  • One or more kinds of acids are optionally selected from the above-mentioned organic acids depending on the metal elements constituting the metal impurities.
  • a wavelength of light to be irradiated to the semiconductor substrate is at least 500 nm, preferably 400 to 900 nm, more preferably 600 to 700 nm. If it is less than 500 nm, a photocatalytic effect near to the surface of the semiconductor substrate is weak and the organic acid is not to be reduced and dissociated. Further, the higher the intensity of illumination of light is, the larger the irradiated dose is, so that the amount of bringing carriers into existence becomes large and reduction and dissociation of the organic acid are promoted. According the above, it can be considered that a complex ion-forming ability is improved and an effect of removing metal impurities near to the surface of the substrate is heightened.
  • the mixed solution of the first washing step is preferably a washing solution relating to Claim 1.
  • a dissolved ozone aqueous solution there may be mentioned a dissolved ozone aqueous solution, hydrogen peroxide solution or nitric acid.
  • the dissolved ozone aqueous solution is preferred since it is high purity, high oxidizing power with a low concentration and easily available.
  • An ozone concentration of the dissolved ozone aqueous solution is preferably 0.5 ppm or more. If it is less than 0.5 ppm, it is difficult to form a hydrophilic oxidized film on the surface of the substrate, and decomposition and removal effects of organic acids or organic substances adhered to the surface of the substrate are lowered. Since a dissolution limit of ozone to pure water is about 25 ppm, the ozone concentration of the dissolved ozone aqueous solution is more preferably 5 to 25 ppm.
  • a silicon wafer is washed with a high concentration hydrofluoric acid, a naturally oxidized film on the surface of the wafer is removed and about 90 % of the surface of the wafer is terminated by hydrogen atom.
  • a surface potential of the wafer is lowered and Cu, Ni, etc. which easily form a silicide accept an electron from the surface of the wafer to adhere to the surface of the wafer. Easiness of transfer the electron to an ion species such as a Cu ion, etc. from the surface of the wafer depends on an interfacial level in the solution.
  • the interfacial level thereof is in the state near to that of the silicon wafer and electrons transfer through an electron transitional step so that this kind of a metal ion transfers to the surface of the wafer.
  • adhesion and deposition phenomenon of the metal can be considered to be a complex system of the above-mentioned (a) as a base. That is, depending on how much amounts of hydrofluoric acid and an organic acid is present in the washing solution, the above-mentioned adhesion and deposition phenomenon will change. As a factor to determine the adhesion phenomenon, there are dissociation constant or ionization constant of the acid. When the constant is large, much amounts of protons are released and ion species of the acid increase. In the mixed system of hydrofluoric acid and an organic acid, it can be considered that an acid having a larger dissociation constant will be more predominantly dissociated.
  • an amount of HF molecules which are not dissociated is also increased so that the naturally oxidized film is removed and a metal which easily forms a silicide such as Cu becomes to be easily adhered and deposited.
  • a metal which easily forms a silicate such as Fe also becomes to be easily adhered and deposited.
  • the metal such as Fe becomes to be easily formed due to increase in the concentration of the organic acid and an adhered amount to the surface of the wafer is lowered.
  • citric acids As shown in Table 1, as an organic acid, 0.0006 % by weight, 0.006 % by weight and 0.06 % by weight of citric acids were mixed with pure water, respectively. To a citric acid aqueous solution containing 0.0006 % by weight of the acid were added 0.005 % by weight, 0.05 % by weight and 0.25 % by weight of hydrofluoric acid, respectively, to prepare washing solutions. Also, to a citric acid aqueous solution containing 0.006 % by weight of the acid were added 0.005 % by weight, 0.05 % by weight and 0.25 % by weight of hydrofluoric acid, respectively, to prepare washing solutions.
  • EDTA ethylenediaminetetraacetic acids
  • Table 2 As shown in Table 2, as an organic acid, 0.00008 % by weight and 0.0008 % by weight of ethylenediaminetetraacetic acids (EDTA) were mixed with pure water, respectively.
  • EDTA aqueous solution containing 0.00008 % by weight of the acid were added 0.005 % by weight, 0.05 % by weight and 0.25 % by weight of hydrofluoric acid, respectively, to prepare washing solutions.
  • washing solutions pH of the respective washing solutions are shown in Table 4.
  • a silicon wafer cleaned by another SC1 solution was immersed, heated to 75 to 80 °C and maintained at 80 °C for 10 minutes. After this silicon wafer was rinsed by ultrapure water, the wafer was immersed in a mixed solution of H 2 O:
  • a washing solution was prepared by adding 1 % by weight of hydrofluoric acid to a solution prepared by mixing 0.005 % by weight of ethylenediaminetetraacetic acid as an organic acid with pure water and pH of the solution was adjusted to 1.
  • To the washing solution were added metal ions and fine particles which are similar to those used in Examples with the same amounts, and then a silicon wafer was immersed in the washing solution for 10 minutes. Thereafter, the silicon wafer was rinsed by ultrapure water in the same manner as in the above-mentioned Examples and dried.
  • a washing solution was prepared by adding 0.05 % by weight of hydrofluoric acid to pure water. To the washing solution were added metal ions and fine particles which are similar to those used in Examples with the same amounts, and then a silicon wafer was immersed in the washing solution for 10 minutes. Thereafter, the silicon wafer was rinsed by ultrapure water in the same manner as in the above-mentioned Examples and dried.
  • a washing solution was prepared by adding 0.25 % by weight of hydrofluoric acid to pure water. To the washing solution were added metal ions and fine particles which are similar to those used in Examples with the same amounts, and then a silicon wafer was immersed in the washing solution for 10 minutes. Thereafter, the silicon wafer was rinsed by ultrapure water in the same manner as in the above-mentioned Examples and dried.
  • Metal impurities concentrations were measured on the surface of the silicon wafers after washing them with washing solutions prepared in Examples 1 to 4, 7 to 11, 14, 15, 17, 18, 21 to 23, 26 to 29, 31, 34, 35, 37 to 42 and Comparative example 1. These metal impurities concentrations were measured by dropping a mixed acid of hydrofluoric acid and nitric acid to the center portion of the silicon wafer after washing, and after developing liquid drops to cover the whole surface of the silicon wafer, and recovering the liquid drops to analyze them by atomic-absorption spectroscopy. The results are shown in Table 1 to Table 3.
  • the number of remained particles on the surface of the respective wafers after washing them with each of washing solutions prepared in Examples 1, 4, 7, 12, 15, 18, 20, 22, 24, 26, 31 and Comparative examples 1 to 4 was measured.
  • the number of remained particles was measured by counting particles with a particle size of 0.2 ⁇ m or more remained on the surface of the silicon wafer after washing with a particle counter. The results are shown in Table 4 and Table 5.
  • a washing solution in which 0.006 % by weight of citric acid was added to pure water as an organic acid, having pH of 4.0 was prepared.
  • the above-mentioned metal-contaminated silicon wafer was immersed in the washing solution at room temperature for 10 minutes, and irradiated light having an intensity of illumination of 100,000 lux and a wavelength of 500 nm to the surface of the silicon wafer. Thereafter, this silicon wafer was rinsed with ultrapure water for 10 minutes. According to the above procedure, peeling off of a naturally oxidized film on the surface of the wafer, complexing ions of metal impurities and control of each surface potential of the wafer, fine particles and metal impurities were carried out as mentioned above to clean the silicon wafer.
  • Example 43 In the same manner as in Example 43 except for changing the wavelength of the light to be irradiated to 550 nm, a silicon wafer was washed.
  • Example 43 In the same manner as in Example 43 except for changing the wavelength of the light to be irradiated to 600 nm, a silicon wafer was washed.
  • Example 43 In the same manner as in Example 43 except for changing the wavelength of the light to be irradiated to 650 nm, a silicon wafer was washed.
  • Example 43 In the same manner as in Example 43 except for changing the wavelength of the light to be irradiated to 450 nm, a silicon wafer was washed.
  • Fe concentrations on the surfaces of the silicon wafers of Examples 43 to 46 and Comparative examples 5 and 6 after washing were examined. These metal impurities concentrations were measured by dropping a mixed acid of hydrofluoric acid and nitric acid to the center portion of the silicon wafer after washing, and after developing liquid drops to cover the whole surface of the silicon wafer, and recovering the liquid drops to analyze them by atomic-absorption spectroscopy. The results are shown in Fig. 4.
  • a silicon wafer to the surface of which is adhered five metal of Al, Fe, Cu, Ni and Zn previously was prepared by the following method.
  • This solution was raised to 80 °C, and after immersing the silicon wafer in the solution at 80 °C for 10 minutes, the wafer was rinsed for 10 minutes, then it was rinsed and water drops on the surface of the wafer were removed by centrifugal force and dried.
  • a mixed solution was prepared by adding 0.05 % by weight of hydrofluoric acid to a solution in which 0.006 % by weight of citric acid was added to pure water as an organic acid, and adjusted to pH 3.0 was prepared.
  • the mixed solution at room temperature was immersed the silicon wafer contaminated by the above-mentioned metal impurities and then washed under ultrasonic wave for 10 minutes. Thereafter, this silicon wafer was rinsed with ultrapure water for 10 minutes.
  • this washed silicon wafer was immersed in a dissolved ozone aqueous solution with an ozone concentration of 8 ppm for 10 minutes. Thereafter, this silicon wafer was rinsed with ultrapure water for 10 minutes.
  • the silicon wafer was washed again with the above-mentioned first washing step, and then washed again with the above-mentioned second washing step. That is, the first washing step and the second washing step were each carried out twice, respectively.
  • Metal impurities concentrations on each surface of the respective silicon wafers after washing of Example 47 and Comparative example 7 were measured. This metal impurities concentrations were measured by dropping a mixed acid of hydrofluoric acid and nitric acid to the center portion of the silicon wafer after washing, and after developing liquid drops to cover the whole surface of the silicon wafer, and recovering the liquid drops to analyze them by atomic-absorption spectroscopy. The results are shown in Fig. 5. As clearly seen from Fig. 5, it can be found that, in the wafer of Example 47, except for Ni concentration which was the same level, there are good washing effects with regard to the other five kinds of metals with the order of one digit as compared with the wafer of Comparative example 7 according to the conventional RCA washing method. Particularly, four kinds of metals of Al, Fe, Ni and Zn were each 10 ⁇ 10 8 atoms/cm 2 or less. Incidentally, an arrow to downward of Fe and Ni means lower than detection limit.
  • the photoirradiation brings minority carrier into existence near to the substrate surface, which reduces and dissociates an organic acid in the washing solution to make metal impurities into metal complex salts whereby an effect of removing metal impurities near to the surface of the substrate can be heightened.
  • Chemical solution for washing is only one kind of an organic acid alone, or two kinds of hydrofluoric acid and an organic acid.
  • washing method of the invention relating to Claim 8
  • three actions of peeling a naturally oxidized film on the surface of the substrate, complex ionization of metal impurities, and control of each surface potential of the substrate, fine particles and metal impurities can be carried out in the first washing step to remove both of metal impurities and fine particles well from the semiconductor substrate, and then, in the second step, an oxidized film is formed on the surface of the substrate and simultaneously an organic acid or an organic material adhered to the surface of the substrate is decomposed and removed.
  • both of metal impurities and fine particles can be well removed, and chemical solutions for washing may be only three kinds of hydrofluoric acid solution and an oxidizing solution.

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  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
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  • Cleaning By Liquid Or Steam (AREA)
EP98100625.7A 1997-01-16 1998-01-15 Waschlösung für Halbleiter-Substraten und Waschmethode Expired - Lifetime EP0859404B1 (de)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
JP5612/97 1997-01-16
JP5610/97 1997-01-16
JP561097 1997-01-16
JP5611/97 1997-01-16
JP561197A JPH10209100A (ja) 1997-01-16 1997-01-16 半導体基板の洗浄方法
JP00561297A JP3354822B2 (ja) 1997-01-16 1997-01-16 半導体基板の洗浄方法

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EP0859404A2 true EP0859404A2 (de) 1998-08-19
EP0859404A3 EP0859404A3 (de) 1999-05-26
EP0859404B1 EP0859404B1 (de) 2014-04-02

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EP0982765A2 (de) * 1998-08-28 2000-03-01 Mitsubishi Materials Silicon Corporation Verfahren zur Reinigung eines Halbleitersubstrats
EP1005072A1 (de) * 1998-11-19 2000-05-31 Wacker Siltronic Gesellschaft für Halbleitermaterialien Aktiengesellschaft Verfahren zur nasschemischen Behandlung von Halbleiterscheiben
FR2796319A1 (fr) * 1999-07-13 2001-01-19 Lionel Girardie Procede de nettoyage et de gravure de semi-conducteurs
US6303551B1 (en) 1997-10-21 2001-10-16 Lam Research Corporation Cleaning solution and method for cleaning semiconductor substrates after polishing of cooper film
US6358847B1 (en) 1999-03-31 2002-03-19 Lam Research Corporation Method for enabling conventional wire bonding to copper-based bond pad features
EP1189265A1 (de) * 2000-03-17 2002-03-20 Shin-Etsu Handotai Co., Ltd Wasser für die aufbewahrung von siliziumscheiben und aufbewahrungsmethode
EP1196943A1 (de) * 1999-05-26 2002-04-17 Ashland Inc. Verfahren für das entfernen von verunreinigungen von der oberfläche und dafür nützliche zusammensetzungen
US6479443B1 (en) 1997-10-21 2002-11-12 Lam Research Corporation Cleaning solution and method for cleaning semiconductor substrates after polishing of copper film
US6593282B1 (en) 1997-10-21 2003-07-15 Lam Research Corporation Cleaning solutions for semiconductor substrates after polishing of copper film
EP1536291A1 (de) * 2002-08-22 2005-06-01 Daikin Industries, Ltd. Entfernungslösung
WO2007045269A1 (en) * 2005-10-21 2007-04-26 Freescale Semiconductor, Inc. Method for cleaning a semiconductor structure and chemistry thereof
US7312159B2 (en) 2000-08-31 2007-12-25 Micron Technology, Inc. Compositions for dissolution of low-k dielectric films, and methods of use
WO2008053705A2 (en) * 2006-10-24 2008-05-08 Asahi Glass Company, Limited Method for removing foreign matters from substrate surface

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JP3510562B2 (ja) * 2000-04-28 2004-03-29 Necエレクトロニクス株式会社 半導体装置の製造方法及び処理装置
EP1389496A1 (de) * 2001-05-22 2004-02-18 Mitsubishi Chemical Corporation Verfahren zur reinigung einer substratfläche
US6610599B1 (en) * 2002-06-19 2003-08-26 Lucent Technologies Inc. Removal of metal veils from via holes
JP2004253775A (ja) * 2003-01-31 2004-09-09 Nec Electronics Corp 化学機械的研磨方法
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181623A (en) * 1977-03-15 1980-01-01 Colgate-Palmolive Company Cleaning compositions
EP0571950A2 (de) * 1992-05-29 1993-12-01 Texas Instruments Incorporated Entfernung von metallischer Verunreinigung
WO1994027314A1 (en) * 1993-05-13 1994-11-24 Interuniversitair Microelektronica Centrum Method for semiconductor processing using mixtures of hf and carboxylic acid
US5382296A (en) * 1991-02-27 1995-01-17 Okmetic Oy Method for cleaning semiconductor products
EP0674343A2 (de) * 1994-03-25 1995-09-27 Shin-Etsu Handotai Company Limited Verfahren zum Lagern von Silizium-Wafern
FR2722511A1 (fr) * 1994-07-15 1996-01-19 Ontrak Systems Inc Procede pour enlever les metaux dans un dispositif de recurage
DE19521389A1 (de) * 1994-12-06 1996-06-13 Mitsubishi Electric Corp Verfahren und Vorrichtung zum Herstellen einer integrierten Halbleiterschaltung
WO1996026538A1 (en) * 1995-02-21 1996-08-29 Advanced Micro Devices, Inc. Chemical solutions for removing metal-compound contaminants from wafers after cmp and the method of wafer cleaning
DE19515024A1 (de) * 1995-04-24 1996-10-31 Wacker Siltronic Halbleitermat Reinigungsmittel und Verfahren zum Reinigen von Halbleiterscheiben

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5409544A (en) * 1990-08-20 1995-04-25 Hitachi, Ltd. Method of controlling adhesion of fine particles to an object in liquid
US5695569A (en) * 1991-02-28 1997-12-09 Texas Instruments Incorporated Removal of metal contamination
JP2652320B2 (ja) * 1993-03-31 1997-09-10 住友シチックス株式会社 シリコンウェーハの洗浄方法
JP2914555B2 (ja) * 1994-08-30 1999-07-05 信越半導体株式会社 半導体シリコンウェーハの洗浄方法
US5714203A (en) * 1995-08-23 1998-02-03 Ictop Entwicklungs Gmbh Procedure for the drying of silicon

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4181623A (en) * 1977-03-15 1980-01-01 Colgate-Palmolive Company Cleaning compositions
US5382296A (en) * 1991-02-27 1995-01-17 Okmetic Oy Method for cleaning semiconductor products
EP0571950A2 (de) * 1992-05-29 1993-12-01 Texas Instruments Incorporated Entfernung von metallischer Verunreinigung
WO1994027314A1 (en) * 1993-05-13 1994-11-24 Interuniversitair Microelektronica Centrum Method for semiconductor processing using mixtures of hf and carboxylic acid
EP0674343A2 (de) * 1994-03-25 1995-09-27 Shin-Etsu Handotai Company Limited Verfahren zum Lagern von Silizium-Wafern
FR2722511A1 (fr) * 1994-07-15 1996-01-19 Ontrak Systems Inc Procede pour enlever les metaux dans un dispositif de recurage
DE19521389A1 (de) * 1994-12-06 1996-06-13 Mitsubishi Electric Corp Verfahren und Vorrichtung zum Herstellen einer integrierten Halbleiterschaltung
WO1996026538A1 (en) * 1995-02-21 1996-08-29 Advanced Micro Devices, Inc. Chemical solutions for removing metal-compound contaminants from wafers after cmp and the method of wafer cleaning
DE19515024A1 (de) * 1995-04-24 1996-10-31 Wacker Siltronic Halbleitermat Reinigungsmittel und Verfahren zum Reinigen von Halbleiterscheiben

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ANONYMOUS: "Silicon Surface Cleaning Process. October 1977." IBM TECHNICAL DISCLOSURE BULLETIN, vol. 20, no. 5, October 1977, pages 1746-1747, XP002095501 New York, US *
PATENT ABSTRACTS OF JAPAN vol. 095, no. 001, 28 February 1995 & JP 06 291099 A (SUMITOMO SITIX CORP), 18 October 1994 *

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999021220A1 (en) * 1997-10-21 1999-04-29 Ontrak Systems, Inc. Methods and apparatus for cleaning semiconductor substrates after polishing of copper film
US6162301A (en) * 1997-10-21 2000-12-19 Lam Research Corporation Methods and apparatus for cleaning semiconductor substrates after polishing of copper film
US6165956A (en) * 1997-10-21 2000-12-26 Lam Research Corporation Methods and apparatus for cleaning semiconductor substrates after polishing of copper film
US6593282B1 (en) 1997-10-21 2003-07-15 Lam Research Corporation Cleaning solutions for semiconductor substrates after polishing of copper film
US6479443B1 (en) 1997-10-21 2002-11-12 Lam Research Corporation Cleaning solution and method for cleaning semiconductor substrates after polishing of copper film
US6303551B1 (en) 1997-10-21 2001-10-16 Lam Research Corporation Cleaning solution and method for cleaning semiconductor substrates after polishing of cooper film
KR100340274B1 (ko) * 1998-08-28 2002-06-12 가와이 겐이찌 반도체 기판의 세정 방법
EP0982765A2 (de) * 1998-08-28 2000-03-01 Mitsubishi Materials Silicon Corporation Verfahren zur Reinigung eines Halbleitersubstrats
EP0982765A3 (de) * 1998-08-28 2000-04-19 Mitsubishi Materials Silicon Corporation Verfahren zur Reinigung eines Halbleitersubstrats
US7172975B2 (en) 1998-11-19 2007-02-06 Siltronic Ag Process for the wet chemical treatment of semiconductor wafers
SG83159A1 (en) * 1998-11-19 2001-09-18 Wacker Siltronic Halbleitermat Process for the wet chemical treatment of semiconductor wafers
EP1005072A1 (de) * 1998-11-19 2000-05-31 Wacker Siltronic Gesellschaft für Halbleitermaterialien Aktiengesellschaft Verfahren zur nasschemischen Behandlung von Halbleiterscheiben
US6358847B1 (en) 1999-03-31 2002-03-19 Lam Research Corporation Method for enabling conventional wire bonding to copper-based bond pad features
US6610601B2 (en) 1999-03-31 2003-08-26 Lam Research Corporation Bond pad and wire bond
EP1196943A1 (de) * 1999-05-26 2002-04-17 Ashland Inc. Verfahren für das entfernen von verunreinigungen von der oberfläche und dafür nützliche zusammensetzungen
EP1196943A4 (de) * 1999-05-26 2007-01-17 Air Prod & Chem Verfahren für das entfernen von verunreinigungen von der oberfläche und dafür nützliche zusammensetzungen
FR2796319A1 (fr) * 1999-07-13 2001-01-19 Lionel Girardie Procede de nettoyage et de gravure de semi-conducteurs
EP1189265A4 (de) * 2000-03-17 2007-04-25 Shinetsu Handotai Kk Wasser für die aufbewahrung von siliziumscheiben und aufbewahrungsmethode
EP1189265A1 (de) * 2000-03-17 2002-03-20 Shin-Etsu Handotai Co., Ltd Wasser für die aufbewahrung von siliziumscheiben und aufbewahrungsmethode
US7432214B2 (en) 2000-08-31 2008-10-07 Micron Technology, Inc. Compositions for dissolution of low-k dielectric film, and methods of use
US8951433B2 (en) 2000-08-31 2015-02-10 Micron Technology, Inc. Compositions for use in semiconductor devices
US7312159B2 (en) 2000-08-31 2007-12-25 Micron Technology, Inc. Compositions for dissolution of low-k dielectric films, and methods of use
US8632692B2 (en) 2000-08-31 2014-01-21 Micron Technology, Inc. Compositions for use in semiconductor devices
US7399424B2 (en) * 2000-08-31 2008-07-15 Micron Technology, Inc. Compositions for dissolution of low-k dielectric films, and methods of use
US8142673B2 (en) 2000-08-31 2012-03-27 Micron Technology, Inc. Compositions for dissolution of low-k dielectric films, and methods of use
US7521373B2 (en) 2000-08-31 2009-04-21 Micron Technology, Inc. Compositions for dissolution of low-k dielectric films, and methods of use
EP1536291A1 (de) * 2002-08-22 2005-06-01 Daikin Industries, Ltd. Entfernungslösung
US7833957B2 (en) 2002-08-22 2010-11-16 Daikin Industries, Ltd. Removing solution
EP1536291A4 (de) * 2002-08-22 2008-08-06 Daikin Ind Ltd Entfernungslösung
WO2007045269A1 (en) * 2005-10-21 2007-04-26 Freescale Semiconductor, Inc. Method for cleaning a semiconductor structure and chemistry thereof
WO2008053705A3 (en) * 2006-10-24 2008-09-18 Asahi Glass Co Ltd Method for removing foreign matters from substrate surface
US8052797B2 (en) 2006-10-24 2011-11-08 Asahi Glass Company, Limited Method for removing foreign matter from substrate surface
WO2008053705A2 (en) * 2006-10-24 2008-05-08 Asahi Glass Company, Limited Method for removing foreign matters from substrate surface

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EP0859404A3 (de) 1999-05-26
US6296714B1 (en) 2001-10-02

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